Copolymers of isopropenyl acetate and fumaric or maleic ester-amides



Patented Oct. 25, 1949 COPOLYMERS OF ISOPROPENYL ACETATE AND FUMARIC OR-MALEIC ESTER-AMIDES William 0. Kenyon and Cornelius C. Unruh,Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N, Y.,a corporation of New Jersey No Drawing. Application August 13, 1947,

This invention relates to copolymers of isopropenyl acetate and fumaricor maleic esteramides.

In our copending application Serial No. 495,888, filed July 23, 1943(now United States Patent 2,448,531, dated September 7, 1948), we haveshowed that although isopropenyl acetate cannot be homopoly-merized togive a high molecular weight resinous homopolyuner, it can becopolymerized with one or more esters of furnaric or maleic acid to givevery useful resinous copolymers. We have now found that isopropenylacetate can be copolymerized with fumaric or maleic ester-amides to giveuseful resinous copolymers.

It is, accordingly, an object of our invention to provide new resinouscopolymers. A further object is to provide a process for preparing suchpolymers. Other objects will become apparent hereinafter,

In accordance with our invention, we copolymerize isopropenyl acetatewith at least one ester,- amide of 'one ofthe following generalformulas:

(maleic ester-amide) (lumaric ester-amide) wherein R represents aradical of a monohydric alcohol, and R and R each represents a memberselected from the group consisting of hydrogen and a radical of amonohydric alcohol. Isop-ro |penyl acetate can be represented by thefollowing formula:

The eopolymerization of isopropenyl acetate with the ester-amides isaccelerated by heat, and by the polymerization catalysts which are knownto accelerate the polymerization of vinyl and acrylic compounds.Exemplary of such catalysts are the organic peroxides (e. g. benzoylperoxide, acetyl peroxide and lauroyl peroxide), hydrogen peroxide,perborates (e. g. alkali metal perborates) and persulfates (e. g. alkalimetal persulfates).

The copolymerization can be effected with or without a diluent. Thediluent, if employed, is advantageously a solvent for the copolymer. Themonomers can also be emulsified in a liquid in which they are insoluble(e. g. water) and the emulsion subjected to polymerization. The monomerscan also be suspended in water using rela- Serial No. 768,513

8 Claims. (01. 26078) tively poor dispersing agents, such as starch, and

polymerized in the form of granules. The proportions of isopropenylacetate and the esteramide in the polymerization mixtures can be variedwidely and still give copolymers in which the molar ratio of isopropenylacetate to the esteramide is substantially 1:1. While the polymerizationmixtures containing from 1 to 9 parts by eight of isopropenyl acetate tofrom 9 to 1 parts by weight of the ester-amide give good copolymers in1:1ratio, the most satisfactory process and the best copolymers areobtained with polymerization mixtures containing from 1 to 3 parts byweight of isopropenyl acetate to 1 part by weight of the ester-amide.

The ester-amides in which R in the above formulas represents an alkylgroup of the formula CnH2n+1 wherein n represents a positive integer offrom one to four, and in which R and R" represents hydrogen or an alkylgroup of the formula CnH2n+1 wherein n represents a positive integer offrom 1 to 4, give copolymers of particular utility for molding purposes.

Not only ester-amides in which the aforesaid alcohol radicals areCnH2n+1 groups wherein n represents a positive integer, can be used, butalso ester-amides containing substituted alcohol radicals, unsaturatedalcohol radicals, e. g. allyl, 13- chlorethyl, fl-ethoxyethyl, can alsobe used.

The following examples will serve to illustrate our new resinouscopolymers and the manner of obtaining the same.

Example 1.C'opolymer of isopropenyl acetate and ethyl fumaramate (a) 5parts by weight of isopropenyl acetate, 7.2 parts by weight of ethylfumaramate, 0.06 part by weight of benzoyl peroxide and 20 parts byvolume of dry dioxane were sealed together in a glass ampoule and placedin a 0. constant temperature bath. A clear, colorless solution formedafter a few minutes, and after 24 hours it had changed to a clear,colorless viscous mass. After another 48 hours, the product was thinnedwith dioxane containing 10 per cent of Water, and the. diluted solutionpoured into an excess of methanol. The white precipitate thus 4 obtainedwas redissolved in a dioxane-water mixture and reprecipitated intomethanol. The yield was 11 parts of a white polymer. Analysis fornitrogen indicated that the molar ratio of isopropenyl acetate to ethylfumaralmate in the co- !polymer was 1:1.02.

(b) 5 parts by weight of isopropenyl acetate, 7.2 parts by weight ofethyl fumaramate and 0.05 part by weight or benzoyl peroxide were sealedin a glass ampoule and placed in a. steam bath. In a short while, thesolution had become homogeneous, and within 15 minutes had changed to avery viscous, yellow colored mass, which hardened at the end of 2 hours.The mass was dissolved in dioxane containing 10 per cent of water andthe solution poured into an excess of agitated methanol. This wasdissolved in wet dioxane and reprecipitated in methanol and dried at 50C. The yield 01 polymer was 9.5 parts. Analysis for nitrogen indicatedthat the molar ratio of isopropenyl acetate to ethyl iumaramate in thecopolymer was 1:0,97.

Example 2.-Cpol1!mer of isopropenyl acetate and N-butyl ethyl jumaramate5.0 grams of isopropenyl acetate, 10.0 grams oi N-butyl ethyl fumaramateand 0.15 gram of benzoyl peroxide were sealed together in a glass tubeand placed in a 50 0. bath. Alter heating in the bath at thistemperature for a period o! days. the contents of the tube had changedto a clear, hard and slightly yellow colored resin, which was soluble inacetone. The unchanged monomers were removed by dissolving the resin inacetone, filtering the solution and reprecipitating into an excess ofboiling hydrocarbon fraction having a boiling range of 105 to 156 F, Thepurification step was repeated once more, the resin being dried undervacuum. This was followed by dissolving the precipitate a third time inacetone and pouring the solution into hot water. at 50 C. The yield ofresin was 11.5 grams. The analysis for nitrogen gave 4.70 per cent byweight as compared with calculated theory of 4.66 per cent, indicatingby this result that a substantially pure copolymer in the ratio of onemole of isopropenyl acetate to one mole oi N-butyl ethyl fumaramate hadbeen obtained.

Example 3.-C'opolymer of isopropenyl acetate and N-diethul ethyljumaramate 10.0 grams of isopropenyl acetate, 19.9 grams of N-diethylethyl fumaramate and 0.15 gram of benzoyl peroxide were sealed togetherin a glass tube and placed in a 50 C. bath. After heating in the bath atthis temperature for a period of 30 days, the contents of the tube hadchanged to a viscous, light brown colored liquid. This was diluted withacetone, filtered and the solution poured into boiling hydrocarbonfraction having a boiling range of 105 to 156 F. The precipitateobtained was redissolved and reprecipitated as above. It was then driedin vacuo at 50 C. Analysis of the resin gave 'a nitrogen contentslightly greater than the theoretical of 4.66 per cent by weight,indicating thereby that the resin obtained was substantially a copolymerin the ratio of one molecular weight of isopropenyl acetate to onemolecular weight of N-diethyl ethyl fumaramate.

Example 4.--Copolymer of isopropenyl acetate and ethyl maleamate 5 partsby weight of isopropenyl acetate, 72.

50 C. constant temperature bath and agitated for a few minutes, until aclear, colorless solution formed, and allowed to stand in the bath for24 hours. A clear, colorless, non-flowing mass The white precipitate wasdried in'vacuo,

dioxane containing about 10 p r cent of water, and the diluted solutionpoured into excess of agitated methanol. The white precipitate thusobtained was redissolved in a dioxane-wa'ter mixtureand reprecipitatedi'nto methanol. The polymer was dried at 50 C. A yield of 11 parts byweight 01 the polymer was obtained. Analysis for nitrogen indicated thatthe molar ratio oi isopropenyl acetate to ethyl maleamate in thecopolymer was approximately 1:1.

In the above example, the ethyl malcamate was prepared by bubbling dryammonia as through a solution of 150 gms. oi maleic anhydride in 3liters of dry benzene which was kept cold in an ice bath. when no moreammonia appeared to be absorbed, the white precipitate which had formedwas filtered oil and dried. This product was dissolved in 3 liters ofdistilled water, filtered and 'to the filtrate 250 gms. of silvernitrate in 600 cc. of distilled water were added. In a few minutes, avoluminous white precipitate formed, which was filtered oil by suctionand dried at 55 0. Care was taken not to expose this silver salt tobright light. 100

gms. of the above silver salt were pulverized and then suspended in 300cc. of dry benzene, and to the well stirred suspension 65 gms. of ethyliodide were added. The mixture was heated under reflux on a steam bathfor one-halt hour and filtered while still hot. The filtrate, oncooling, precipitated long, slender needles. After separation anddrying, the crystals were recrystallized from a mixture of equal partsotbenzene and petroleum ether, decolorizing with charcoal at the sametime. The purified, white, silky needies had a melting point of 95 C.The yield was about 25 grams. Analysis of the product gave by weight50.28 per cent carbon, 6.35 per cent hydrogen and 9.68 per cent nitrogencompared with calculated theory of 50.34 per cent, 6.34 per cent and9.78 per cent, respectively. This indicated that a substantially pureethyl maleamate had been obtained.

Although in each of the above examples only a single ester-amide iscopolymerized with isopropenyl acetate, ,it willbe understood that morethan one ester-amide of fumaric acid, more than one ester-amide ofmaleic acid can be copolymerized with isopropenyl acetate, or, anester-amide of fumaric acid and an ester-amide of maleic acid can becopolymerized with isopropenyl acetate simultaneously. Otherester-amides than those illustrated in the examples also are con- 1templated in the invention. In addition to the ester-amides alreadymentioned, there may be employed equivalent amounts in the aboveexamples of the methyl, propyl, butyl, allyl, p-chloroethyl orB-ethoxyethyl iumaramates and corresponding maleamates, and the N-alkylderivatives such as N-methyl, N,N-dimethyl, N-ethyl, N,N-diethyl,N-propyl, N,N-dipropyl', N-butyl, N,N-dibutyl, N-allyl, N,N-diallyl,N-pchloroethyl, N,N-di-fi-chloroethyl, N-fi-ethoxyethyl,N,N-di-fi-ethoxyethyl of the above-mentioned fumaramates and maleamates.

The various ester-amides of fumaric acid can be prepared from the acidmonoester chlorides by reacting the chlorides with ammonia or with thedesired alkylamine, by condensing the monoamide chloride with thedesired monohydric alcohol or by methods described in BeilsteinsHandbuch der Organlschen Chemie, 4th edition, vol. 2, page 743; vol. 4,page 63; and vol. 12, page 305. A number of the ester-amides of maleicacid can was obtained. Thiswas thinnedbythe additionoi also be preparedby the method described in Example 4 wherein ethyl maleamate is obtainedfrom the reaction of gaseous ammonia with maleic anhydride.

What we claim is:

1. A copolymer of isopropenyl acetate and an ester-amide selected fromthe group consisting of a wherein R represents a member selected fromthe group consisting of a radical of a saturated monohydric aliphaticalcohol containing from 1 to 4 carbon atoms and a radical of a mono--hydric olefinic alcohol "containing from 1 to 4 carbon atoms, and R andR" each represents wherein R represents a member selected from the groupconsisting of a radical of a saturated monohydric aliphatic alcoholcontaining from 1 to 4 carbon atoms and a radical of a monohydricolefinic alcohol containing from 1 to 4 carbon atoms, and R and R" eachrepresents a member selected from the group consisting of hydrogen, a.radical of a saturated monohydric aliphatic alcohol containing from 1 to4 carbon atoms and a radical of a monohydric o-lefinic alcoholcontaining from 1 to 4 carbon atoms, which comprises heating a mixtureof from 1 to 3 parts by weight of isopropenyl acetate and 1 part byweight of the said ester-amide, in the presence of a polymerizationcatalyst.

3. A butyl ethyl fumaramate in which the molar ratio of isopropenylacetate to N-butyl ethyl fumaramate is 1:1.

4'. A copolymer of isopropenyl acetate and N- diethyl ethyl fumaramatein which the molar ratio of isopropenyl acetate to N-diethyl ethylfumaramate is 1:1.

5. A copolymer of isopropenyl acetate and ethyl maleamate in which themolar ratio of isopropenyl to ethyl maleamate is 1:1.

6. A process for preparing a 1:1 copolymer of isopropenyl acetate andN-butyl ethyl fumaramate, which comprises heating a mixture of from 1 to3 parts by weight of isopropenyl acetate and 1 part by weight of N-butylethyl fumaramate, in the presence of a polymerization cat alyst.

7. A process for preparing a 1:1 copolymer of isopropenyl acetate andN-diethyl ethyl fumaramate, which comprises heating a mixture of a from1 to 3 parts by weight of isopropenyl acetate and 1 part by weight ofN-diethyl ethyl fumaramate, in the presence of a alyst.

8. A process for preparing a 1:1 copolymerof isopropenyl acetate andethyl maleamate, which comprises heating a mixture of from 1 to 3 partsby weight of isopropenyl acetate and 1' part by weight of ethylmaleamate, in the presence of a polymerization catpolymerizationcatalyst.

WILLIAM O. KENYON. CORNELIUS C. UNRUH.

N 0 references cited.

copolymer of isopropenyl acetate and N-

